Modified acidic copolymer-fatty acid soap greases



United States Patent MODIFIED aAClDIGE (ZOPOLYM-ERrFA'I 'IZY- A011) 1.1SAP.-.. GREASES Johns]. Giammaria, Woodbury,iN. ,.l., ass iguorto $,oc0nyum-9 Gfinl an li aam t adt t a a ati m of NQDr wins- App c ti n. Navei e 7, .195

yS ria No-ilissfl '12 (llaims. (l.*-'252- -39) The present invention relates; to; greasesinv which the gelation a'gentfl sta iqktureoffalkalineearth metal salts ofsacldic; copolymer and --fa tty acids and, more particulady, to greasesl'containin'g atlastflone acidic copolymer,

at leastohejatty ,acidfliaving'jat least -16 carbon atoms, at least one aliphatic, monocarb o rylic acid; having less than six c'arbon atoms 'and an amount 'of at leastv one alkaline earth metal slightly ine'xcess of thatrequired to formed byreacting l'ongchain, aliphatic compounds containing a terminal.

alpha, beta' unsa'turatefd, polycarboxylic acid or anhydride in the presence; of an organic-peroxide. catalyst.

-Ithas been-' ft'trther{disclosed in the aforesaid ico-pend- 'ri ly comp und wh c b used to-form-the acidic copolymerswith the alpha, betaunsaturated polycarboxylic, acids .are aliphatic alpha olefins, allyl esters of aliphatic acids, allyl ethers of aliphatic alcohols, vinyl esters of aliphatic acids and vinyl ethers of. aliphatic} alcohols. ;It; her also been disclosed in the aforesaid col-pending application that the alpha in both of which-R is analkyl radical having at least 10 anduup to'30-carbon atoms, preferably 10.10 22 carbon atoms and especially a' mixture' ayeraging ll8 I'carbon atoms, "areespecially; suitable' for thepreparation of the copolymers per seg the metal sal'ts;ofv'vhich are the novel gel-ling'jage ts. ":Illustrative; of fithe alpha] olefins are ldodecene, ;1-'-hexadecehe, l-octad'ecen'e' ,and higher alpha olefins' and miiitureslthereof:such.as are obtained ,by thermal crackinglof petroleum *wax, pr v'vaxy petroleum stocks 01'' fractions. "Illustrative ofthe allyl esters are allyl laura'te," allyl'-- myris'tate, .allyl ;palm itate, allyl stearate, miXed-fally'l estersysuch, as'gare obtained by esterifying allyl alcohol withhydrogenated'fish fatty acids which contain aliphaticgmonocarbo gylic acidshaving l0 to 22 carbon atoms 5 and, [,ingeneral, allyl estersjobta ined by esterifying allyl alcohol with an aliphatic, monocarboxylic acid'having 10 to 22 carbon atoms.

As disclosed in the Y aforesaid v c -pending application, the'allyl ethers'canbe either the allyl ethers of monohydric or polyhydric alcohols although the ethers of monohydric alcohols oftenor morecarbon atoms are preferred. "Thus, for fexamplegallyl lauryl ether, allyl hexade'cyl'ether, jcthallyl octade'c'ylz ether and thelike can beused.

Of the alpha, beta-unsaturated, aliphatic polycarboxylic acids, the dicarboxylic acids are preferred. Illustrative of they preferred dicarboxylicacids ,are maleic, furnaric, itaconic, .glutaconi c,,mesaconic, ,and .citraconic, and the tri-carboxylic.aconitic acid. While maleic acidin the formof its .anhydride is preferredat thistime, it will be recognized by those ,skilled-in the artthatthe .anhydrides of the acids or acid halides as well; as the ,acids themselves having ,less than I 10 carbon atoms per se can t be .used

although it1is generally ,preferredto use; the vanhydrides in 3 t pr narati 1 t th ta itiic :copolymers.

Patented Dec. 28, 1954 v andan alpha, beta-unsaturated, aliphatic, polycarboxylic acid, especially; a dicarboxylic acid, are the organic per- .oxides" such asbenzoyl peroxide, :di-tertiary-butyl peroxide and lauroyl' perogtide and hydropcrdxides, I such as cumene hydroperoxide.

'f The copolymerization ofgthe aliphatic compound having a terminal vinyl group with an alpha; betaunsaturated, aliphatic, polycarboxylic acid or anhydride is accomplished byheating substantially equi-molarquantities of, the reactants at temperatures within therange of about 75 C. to'abou tf1'50, C. in;the pres ence of aboutiOJ to about 5.0 per cent of per uride, catalyst. Ihe copoly- .rnerizationcan be carried out in the presence or absence of'a solvent such as toluene, xylene, fdioxane, highly acid refined mineral'oilsuch as v vhite oil and the like.

Suitable metals for :thepreparation of :the' novel; class of gelling agents, i; e., the metal salts of the acidic 'copolymer of an aliphatic compound having. a terminal vinyl group and an unsaturated, aliphatic, polycarboxylic acid are the metals of groups LII and Illof'the periodic system. Lithium, calcium, barium. and aluminum salts of the acidic copolymers are preferred.

it was further disclosed in xthe aforesaid 'cmpending application that the aforesaid metal salts of-the acidic copolymers canbe used alone as 'gelation agents orin combination with other gelation agentsxsuch as soaps of conventional fatty or hydroxy fatty V, acids, 7 carbon black, silica, flourand the like.

Thus, for example, it has been disclosedin the aforesaid co-pending application that greases having a very smooth texture can be prepared by converting a mixture of an acidic polymer and ga t'at'ty acid to metal salts in an oleaginous 'vehicle. -Mixtures containing about 10 per cent to about 9 0 per cent offatty acid, and, about 90 per centto about 10 per cent (by weight) of oil-freeacidic copolymers can beused to 'produce the salts which are t the novel mixed gelation agents. .However it is preferred to use about equal parts by weight of an acidic copolymer having a molecular weight of aboutlOOOto about 2000 and a straight-chain, saturated fatty acid. The fatty acids suitabl'eforthis purpose 'aretheindividual fatty acid,.or' mixtures, of fatty acids orhydroxy fatty acids or mixtures of one ormore; fatty acids .and

one or more hydroxy fatty acids; having 10 to, 22 carbon atoms in the molecule such as capric,flauric, stearic, hydroxystearic acid and hydrogenated'fish, oil fatty acids. The acidic copolymer and fatty acid are reacted with .a single metal compound or a plurality of compounds of a plurality of metals of groups I to IV of the periodic systern. Furthermore, the mineral oil vehicle can-beQreplaced wholly orinpartby synthetic oils of the polyester, polyetherandsilicone types. Thus,,for example, the mineral oilvehicle can be replaced whollyoninfpart by an oleaginous vehicle, for example, an ester typesynthetic oil such, as 2-ethylhexyl sebacate, or by a 'polyether synthetic oil such as polyalkylene glycol or. by a silicone such as methylpolysiloxane, orby a polymer oil obtained by/polymerizationof anolefin such as ethylene.

Illustrative of greases having mixed gelation agents comprising the salts of, acidic copolymers and. fatty .acids having 10 to 22 carbon atoms per' molecule disclosedin the aforesaid co-pending application is that of a. grease prepared from a miXtu're o'f 50 parts by weight oil-free acidic coplymer, '50 parts by weight stearic acid, 20 parts by "Weight calcium hydroxide, 1SPQI'IS by Weight water, and 500- parts bywe'ig'ht'of a solvent refined naphthenic oilhaving'aviscosity of 51355 8.- U.- S.Jat' F This grease had-an A.--"S. T. M. penet'ration;@ *77'-F. of

290 (unworked) and 3OO (worked); an A. S. T. M. drop ping point of 237 F. and a water resistance (Spec. It is manifest to'those skilled in the-art'that this is a satisfactory. greaseeXc ept for its'low dropping point. 'The present invention provides ameans for raising the dropping point of this grease. and other greases having-thenovelmixed acidic- 0 polymer salts-fatty. acid saltsgelation agents.

It has been'found that stable greases containing the novel mixed gelation agents and having high dropping points can be obtained by incorporating in the oil blend about 1 to 2% of a low molecular weight fatty acid having less than six carbon atoms and an amount of calcium and/or barium compound capable of neutralizing said low molecular weight fatty acid. Preferably, the calcium and/or barium compound is the hydroxide.

Thus, a high dropping point, smooth textured, stable calcium or barium grease can be prepared from a blend containing about 9 to about 11% by weight of an acidic copolymer of the class described hereinbefore, about 6 to about 8% by weight of a high molecular weight fatty acid and about 1 to about 2% by weight of a low molecular weight fatty acid having less than six carbon atoms in the molecule.

In the aforementioned co-pending patent application it 'was shown that a grease prepared from the calcium salt of an acidic copolymer of the class described had a dropping point in the range of 400 to 500 F. It was also shown therein that, when a mixture of such a copolymer and a high molecular weight fatty acid such as stearic acid was used to prepare a grease containing the calcium salt or salts of the aforesaid copolymer and fatty acid as the gelation agent, the grease was smoother in texture than the grease in which the calcium salt of the acidic copolymer was the sole gelation agent but had a low dropping point in the range of 220 to 270 F.

It will be noted that both greases had a smooth texture and were stable. Consequently, the use of a low molecular weight fatty acid having less than six carbon atoms in the molecule in the presence of a calcium or barium compound capable of neutralizing said low molecular weight acid, i. e., the hydroxide, the

carbonate, etc., to raise the dropping point of a smooth textured, stable grease is not to be confused with the use of a calcium salt of a rnonocarboxylic, aliphatic acid having not more than SlX carbon atoms nor with the use of barium salt of a mineral acid or of a low molecular weight organic acid to stabilize the structure of the normal calcium or barium soap grease as de scribed in U. S. Patents Nos. 2,197,263 and 2,417,433

respectively. That is to say, stabilizing the structure of an unstable grease is not necessarily related to raising the dropping point of an already stable grease.

The dropping point of a smooth textured stable grease prepared from a mixture of an acidic copolymer of the class described hereinbefore and a high molecular weight (1022 carbon atoms) fatty acid is increased from that of about 220 to about 270 F. to about 300 to about 500 F. by incorporating a relatively small amount, say 1% to 2%, of a low molecular weight '(less than six carbon atoms) fatty acid and a neutralizing amount of calcium or barium in the grease mixture.

For economic reasons it is advantageous to substitute for the acidic polymer a substantial amount of fatty acid but the grease so obtained, while satisfactory in every respect, has a limited use because of the relatively low dropping point. By incorporating the low molecular weight fatty acid in the grease, the economic advantages of the smooth textured, stable grease are retained but the dropping point is raised and thus the field of use expanded to its full scope.

As a general procedure, varying proportions of acidic copolymer and high molecular weight fatty acid are blended in a suitable oil base, such as a solvent-refined naphthenic oil, by heating the oil and copolymer-fatty,

acid mixture to about 150 F. The low molecular weight fatty acid, suflicient of the calcium and/ or barium compond to neutralize the three acidic components and a small amount of water are added and the mixture stirred and heated to about 300 to about 400 F. for

a period of time sufiicient to'permit the saponification and dehydration to take place, say about 2 to about 6 hours, and the grease cooled either statically or with agitation.

Accordingly, the grease of the present invention is a tralize acids.

monocarboxylic acid containing 12 to 22 carbon atoms. Preferably these fatty acids are those containing 18 carbon atoms such as a mixture of acids found in fractions of hydrogenated fish oil acids, which have an average of 18 carbon atoms. Small amounts of unsaturated acids can be used but preferably the amount of unsaturated, high molecular weight. fatty acids is limited to 5% or less. The third component is the dropping point increasing material which is a salt of one of the aforesaid metals and an aliphatic, monocarboxylic acid having less than six carbon atoms such as formic acid, acetic acid, butyric acid and valeric acid of which acetic is preferred.

In neutralizing a mixture of the three a'cidic components, complex mixtures of mixed or cross-linked soaps are probably formed rather than the pure soaps of each acidic component.

The proportions of the three acidic components used in preparing the novel high dropping point greases may be varied within fairly wide limits depending upon the types of acidic components, type of oil vehicle, the consistency required, etc. Concentration ranges can vary as follows: about 5 to about 12 weight per cent acidic copolymer; about 5 to about 12 weight per cent high molecular weight fatty acid (12 to 22 carbon atoms) and about 0.5 to about 3' weight per cent low molecular weight fatty acid (less than six carbon atoms).

The total concentration of these three components can vary from about 10 to about 25 weight per cent although, generally, about 15 to about 20 weight per cent is required. For example, when a solvent-refined, naphthenic oil of about 500 S. U. S. F. is employed as the base oil, satisfactory greases are prepared from a mixture comprising about 9 to about 11 weight per cent acidic copolymer, about 6 to about 8 weight per cent of high molecular weight fatty acid and about 1 to about 2 weight per cent low molecular weight fatty acid, i. e., about 16 to about 21 total weight per cent.

The following grease compositions are illustrative of the high dropping point greases of the present inven tion.

EXAMPLE I An acidic copolymer was prepared by copolymerizing maleic anhydride with the allyl ester of distilled, hydrogenated, fish oil acids (available as Hydrofol Acids containing about 77.6% stearic acid, about 17.7% palmitic acid, about 0.5% myristic acid, about 1% arachidic acid and about 3.2 oleic acid. Benzoyl peroxide was used as the catalyst and the copolymerization carried out in the manner described in co-pending application Serial No. 215,859, and hereinbefore. About fifty parts of the resulting oil-free, acidic copolymer, (having a neutralization number of 208), about 50 parts of stearic acid, about 150 parts of acid-refined, naphthenic oil having a viscosity of 232 S. U. S. 100 F. about 350 parts of solvent-refined, naphthenic oil having a viscosity of 513.5 S. U. S. 100 F. were heated to F. in a suitable grease kettle. Ten parts of acetic acid, 24 parts of calcium hydroxide (Ca(OH)z) (4.4 parts excess over theoretical amount required to neu- Represents about 0.5% free CaO in final grease) and 10 parts of water were added and the mixture was heated. The gel which quickly formed became softer at F. 'and fairly fluid at 300 F. The mass began to thicken at 330 F. and finally formed a heavy gel at 400 F. After heating for about 0.5 hour, the source of external heat was removed and the grease was stirred while cooling. Suflicient oil was stirred into the grease at room temperature to give a total content of the three components, i. e., salt or salts'of acidic copolymer, high molecular weight fatty acid and low molecular weight fatty acid, of 19 weight per cent.

EXAMPLE II A mixture of about 50 parts by weight of oil-free, acidic copolymer similar to that used in Example I, having a neutralization 'number of 216, about 50 parts by weight of stearic acid, and about 500 parts by weight of a solvent-refined, naphthenic oil having a viscosity of 513.5 S. U. S. 100 F. was heated to 155 F. in a suitable grease kettle. About 7.5 parts by weight of acetic acid, about 20 parts by weight of Ca(OH) (1.8 parts excess over the theoretical amount required to neutralize acids. Represents about 0.2% free 0:10 in final attests-ts e idi'afi ut .0 a w tep rwaer. we added and the mixture heatd A" soft" gel was"-form'ed at 175 F. which became more fluid at 230 F.- t The mass agaimthickened at about 300 F. and gelled at 315 F. The gel became h'e'avy'andgrairiy at 350 F. and changed to a tough, smooth gel at 360 F. The

temperature was finally raised to 375 F. at which temperature the grease was softer and smoother; The mixture was cooledstatically to 175 F. About'2pa'rts by; weight of 'Ca(OH)z (re resents an additional amount of about .2% CaOin final greaseor a'total of about 0.4% free CaO) were then added and the "grease was stirred while cooling to ambient temperature. The'tota'l salt content was 19 weight per cent.

EXAMPLE III A mixture of about 50 parts-by weight of the oil free copolymerused in Example'Labout '50 partsby weight 'of stearic acid and about 500 parts -byxweight 10f naph thenic oil was heated to about 160 F. in a suitable .grease kettle. About partssby weight of acetic acid, about 18 parts by weight of Ca(OH)z (with the two parts'added later providing about 3.5 parts excess over the theoretical amount required to neutralize acids) and about parts by'weight of water were added and the mixture'was heated'to about 360 F. during a period-of about three hours t to form a smooth grease. It was cooled staticallyto about 200 F. About 2 parts of Ca(OI-I)2 were then added and the grease stirred while cooling to ambient temperature. The total salt content of-the grease Wasabout 18 weight per cent and the free CaO content was about 0.4%.

EXAMPLE IV In the manner described in Examplel, an acidic copolymer of an allyl ester of Hydr'ofol Acids 51 and maleic anhydride was prepared. Hydrofol Acids 51 containabout 8.5% myristie acid, about 35.2% palmitic' acid, about 28.2% stearic acid,-about arachidic' acid, about 8.8% behenic acid, about 1.1% palmitoleic acid, about 1% oleic acid, about l.2%-gadoleic acid and about 1% erucic acid. A mixture of about 50 parts-by weight of this acidic, oil-free copolymer having a neutralization number of 228, about 35 parts by weight of Hydrofol Acids 150 and about 450 parts by weight of a solvent-refined, naphthenic oil was heated to about 160 F. in a grease kettle. About 7 parts by weight of acetic acid, about 17 parts by weight of Ca(OI-I)z, (0.6 part excess) and about 10 parts by weight of water were added and the mixture was heated to about 380 F. during a period of about 4' hours. About 2 parts by weight of Ca(OH)2 were added and the grease cooled with stirring to ambient temperature. The total salt content of the grease was about 18 weight per cent and the free CaO content was about 0.35

EXAMPLE v A mixture of about 50 parts by Weight of the oil-free copolymer used in Example IV, about 35 parts by Weight of Hydrofol Acids 150 and about 450 parts-by weight of solvent-refined, naphthenic oil was heated to about- 170 F. in a grease kettle. About 10 parts by weight of water, about 10.3 parts by weight of butyric acid and about 17 parts by weight of Ca(OH)z (0.6 part excess)- were added and the resultant mixture was heated to 360 F. during a period of about four hours. About 2 parts by weight of Ca(OH)z were added and, after stirring about 10 minutes at about 360 F., the grease was cooled with stirring to ambient temperature. At room temperature the grease was very-soft and grainy. However, it was converted into a smooth texture and stiffer consistency by milling. The total salt content was about 19 weight per cent. The free CaO content of the grease was about 0.35%. p s h EXAMPLE VI Anacidic copolymer was-prepared by polymerizing maleic anhydride with l-octadecene using benzoyl per-' oxide as the catalyst. A mixture of about 36 parts by weight of this acidic copolymer having a neutralization number of 187, about parts by weight of Hydrofol' Acids 150 and about 330 parts by weightof solventrefined, naphthenic oil was heated to about 165" F. in a grease liettle. About 5 parts by weight of 'acetic'acid-,; about-12parts by'weigh't of Ca(OH) (1.3 parts excess) and about 10 parts. by weight of water were added and" the mixture was heated to abouf400 F. during a period of. aboutfive I hours. About one part Ca(QH)z. was added and the greasewascooledto ambient temperature whilst it was stirredl about 0.43%. v p

Toillustrate the'effect of the addition of an aliphatic,

monocarboxylic acid' having less than" six carbon atoiri's'f greases, a grease was upon the dropping point of these prepared without the low. molecular weight ali hatic monoc'arboxylic acid in the manner described in' Ex ample VII.

EXAMPLE VII' A-mixtureof=-about50 parts by weigh-t of.oil-free copolymersimilar to' that used in Example I:('N. N.- 21'6),-v

about 50 parts by, weight of-stearic acid and about 500 parts by weight of solvent-refined, naphthenic oil was heated to about F. in a grease kettle. About eighteen parts by weight of Ca(OH)z (4.4 parts excess) and abou'tlO-p'arts by Weight of water were added and the mixture was heated to about 350 about six hours. The grease wasthen cooled whilst StiI IiI'lgP, The total salt, content was about 18 weight .per

a cent. The excess Ca(OH)z would represent about 0.54%

free CaO in final grease.

The dropping points of the greases prepared as de scribed in Examples'I through- VII are given in table" I.

1 Formulation includes acetic acid. 2 Formulation includes butyric acid.

N0 lowmolecular weight, aliphatic,'monocarboxylic acid.

4 A. S. '1. M. Designation D5b6.

Those skilled in the art will recognize readily that the grease in which no low molecular weight, aliphaticmonocarboxylic acid' was used had a droppingpoint about 160 F. lower than a comparable composition containing a low molecular weight, aliphatic, monocarboxylic acid. Thus, the grease of Example VII in the formulation of which no low molecular weight acid was used had a dropping point of only 230 F., whereas. the greasesin the formulation of which acetic or butyric acid was used had. droppingpoints rangingfrom 325 F. to 490 F. In addition to having high dropping points, the greases containin'gan aliphatic, monocarboxylic acid having less than six'carbon atoms retain the good mechanical stability, the smooth texture, and the absence of a bleeding tendency displayed by theunmodified greases. The modified greases are equivalent to the greases in which the acidic copolymer is the only gelatlon agent in every respect save resistance to oxidation. However, this characteristic can be improved by incorporating an antioxidant, for example phenothiazin'e, in the grease. p

A testfor determining the resistance of greases to oxidation is that having the A. s. T. M. Designation: D442" Tentative Method of Test for Oxidation Stability of Lubricating Greases by the Oxygen Bomb Method. In order to increase the severity of the test, tests were conducted-at 250 F. instead of the standardtemperature of 210 F. These data are shown in table II.

Table 'II MODIFIED. A. s. 'r. M. BOMB TEST FOR. OXIDATION STABILITY on LUBRICA'IING GREASES Hours required Barium ,canzb substituted for calcium inthe aforedes'eribed novel greaseses the. following illustrative but not limiting examples demonstrate.

U The total salt content'was 'about 1:9weight percent,.while the 'free cao content was F. during a period of 7 EXAMPLE VIII A mixture of about 50 parts by weight of the oil-free, acidic copolymer used in Example I, about 35 parts; by Weight of Hydrofol Acids 15 0, about 15 parts by weight of an acid-refined, naphthenic oil having a viscosity of 232 S. U. S. 100 F. and 250 parts of a solvent-refined, naphthenic oil having a viscosity of 513.5 S. U. S. 100 F. was heated in a grease kettle to about 160 F. About 50 parts by weight of Ba(OH)2.8H2O (1.5 parts excess) were added and the mixture was heated to about 415 F. during a period of about 3.5 hours. The source of external heat was removed and the mass was stirred while cooling it to ambient temperature. The total salt content was about 21 weight per cent. The excess barium hydroxide represents about 0.15% BaO in the final grease. The grease had a dropping point of 315 F.

EXAMPLE IX A mixture of about 50 parts by weight of the oil-free, acidic copolymer used in the formulation of the grease described in Example I, about 35 parts by weight of Hydrofol Acids 150, about 150 parts by weight of acidrefined, naphthenic oil having a viscosity of 232 S. U. S. 100 F. and about 300 parts by weight of solvent-refined, naphthenic oil having a viscosity of 513.5 S. U. S. 100 F. was heated to about 160 F. in a grease kettle. About 7 parts by weight of acetic acid and about 70 parts by weight of Ba(OI-I)2.8I-I2O (3.1 parts excess: represents about 0.25% free BaO in final grease) were added and the mixture was heated to about 400 F. during a period of about 3.5 hours. The source of external heat was removed and the mass stirred while cooling to ambient temperature. The total salt content of the grease was about 21 weight per cent. The dropping point of this grease was 470+ F. as compared with 315 F. for the grease of the same formulation, save for the absence of acetic acid, described in Example VIII.

Thus, it is manifest that the addition of an aliphatic monocarboxylic acid having less than six carbon atoms and the stoichiometric equivalent of a group II metal compound capable of reacting with said monocarboxylic acid, for example the hydroxides and carbonates, raises the dropping point of greases containing the novel mixed gelling agents, to wit: salts of a metal of group II of the periodic system and at least one acidic copolymer of the class described hereinbefore and a high molecular weight, saturated, aliphatic, monocarboxylic acid having 12 to 22 and preferably 18 carbon atoms whilst the greases having raised dropping points retain the stability, smooth texture and absence of a tendency to bleed possessed by the greases having low dropping points.

The exact sequence of operations whereby the novel greases of the present invention are prepared, at this time, I

does not seem to be too important. That is to say, the novel greases can be prepared by charging the required amount of acidic copolymer, the required amount of aliphatic, monocarboxylic acid having to 22 carbon atoms and the required amount of aliphatic, monocarboxylic acid having less than 6 carbon atoms together with an amount of basic calcium or barium compound at least suflicient to neutralize all of the acidic components, a small amount of Water and the oleaginous vehicle to a Stable container such as a grease kettle. The mixture is heated to about 300 to 400 F. until a smooth grease is formed. The mixture is then cooled statically or with agitation to ambient temperature.

Alternatively, the required amount of acidic copolymer, the required amount of aliphatic, monocarboxylic acid having 10 to 22 carbon atoms and an amount of basic calcium or barium compound to neutralize the aforesaid acidic components together with the required amount of oleaginous vehicle and a small amount of water are charged to a stable container, for example, a grease kettle. The mixture is heated to about 330 to 400 F. until a smooth grease is formed. The mixture is then cooled to at least 200 F. and an aqueous solution of calcium or barium salt of an aliphatic, monocarboxylic acid having less than 6 carbon atoms is added. The mixture is then heated again to about 300 to 400 F. until the major portion of the water is driven olf and then cooled to ambient temperature with or without agitation.

As those skilled in theart know, a portion of the oleaginous vehicle can be charged to the grease kettle, the

8-. grease formed and suflicient of the oleaginous vehicle" then added tobring the consistency of the grease to the right degree.

Other agents can be incorporated in the basic formulations described hereinbefore. Thus, extreme pressure agents, tackiness agents, inorganic fillers and the like, all well known to those skilled in the art, can be added to the aforedescribed formulations. Inorganic thickening agents such as carbon black and silica flour can be used in combination with the novel gelling agents to reduce the required concentration of the latter to produce a grease of required consistency.

While the illustrative but not limiting examples provided hereinbefore have been typical of formulations of satisfactory greases wherein naphthenic oils were used, those skilled in the art will understand that lubricating fractions of mineral oil from any crude source can be used to replace the naphthenic oils of the illustrative greases wholly or in part.

I claim:

1. A modified grease comprising a major proportion of a lubricating oleaginous vehicle, a minor proportion of a mixed gelling agent and an amount of an aliphatic monocarboxylic acid having less than six carbon atoms and a molar equivalent of a metal of group II of the periodic system sufiicient to provide a grease having a dropping point of at least 300 F., said gelling agent comprising a mixture of salts of a metal of group II of the periodic system and (1) an acidic copolymer of an alpha,beta-unsaturated polycarboxylic acid and an aliphatic compound having a terminal vinyl group, said acidic copolymer having a molecular weight of about 1000 to about 2000, and (2) a saturated aliphatic monocarboxylic acid having 10 to 22 carbon atoms.

2. A grease comprising a mineral lubricating oil fraction, an amount sufiicient to gel said oil fraction to a grease of an aliphatic monocarboxylic acid having 10 to 22 carbon atoms, an acidic copolymer having a molecular weight of about 1000 to about 2000 of an aliphatic compound having a terminal vinyl group and an alpha,betaunsaturated polycarboxylic acid, at least the stoichiometric equivalent of said acid and said acidic copolymer of a metal of group II of the periodic system, and an amount suflicient to raise the dropping point of the said grease of an aliphatic, monocarboxylic acid having less than six carbon atoms and at least a stoichiometric equivalent of a metal of group II of the periodic system.

' 3. A grease comprising a mineral lubricating oil fraction, an amount sufficient to gel said mineral oil fraction to a grease of a mixture of (1) a saturated, aliphatic, monocarboxylic acid having 10 to 22 carbon atoms, (2) an acidic copolymer having a molecular Weight of about 1000 to about 2000 of an aliphatic compound having a terminal vinyl group and an alpha,beta-unsaturated aliphatic polycarboxylic acid having not more than 10 carbon atoms, and (3) at least a stoichiometric equivalent of said aliphatic acid and said acidic copolymer of a metal of group II of the periodic system, and an amount, sufficient to raise the dropping point of the aforesaid grease, of (1) a saturated aliphatic monocarboxylic acid having less than six carbon atoms, and (2) at least the stoichiometric equivalent of said acid having less than six carbon atoms of a metal selected from the group consisting of calcium and barium.

4. A grease comprising about 5 to about 12 weight per cent of an acidic copolymer of an alpha,beta-unsaturated polycarboxylic acid and an aliphatic compound having a terminal vinyl group, said acidic copolymer having a molecular weight of about 1000 to about 2000, about 5 to about 12 weight per cent of a saturated aliphatic monocarboxylic acid having 12 to 22 carbon atoms, at least the stoichiometric equivalent of the foregoing of a metal of group II of the periodic system, about 0.5 to about 3 weight per cent of a saturated aliphatic monocarboxylic acid having less than six carbon atoms, and at least the stoichiometric equivalent of said aliphatic monocarboxylic acid having less than six carbon atoms of a metal selected from the group consisting of calcium and barium, and the tbalance, to make weight per cent, an oleaginous ve- 5. A grease comprising about 5 to about 12 weight per cent of an acidic copolymer of an alpha,beta-unsaturated polycarboxylic acid and an aliphatic compound having a terminal vinyl group, said acidic copolymer having a molecular weight of about 1000 to about 2000, about to about 12 weight per cent of a saturated aliphatic monocarboxylic acid having 12 to 22 carbon atoms, at least the stoichiometric equivalent of the foregoing of a metal of group H of the periodic system, about 0.5 to about 3 weight per cent of a saturated aliphatic monocarboxylic acid having less than six carbon atoms, and at least the stoichiometric equivalent or" said aliphatic monocarboxylic acid having less than six carbon atoms of a metal selected from the group consisting of calcium and barium and the balance, to make 100 weight per cent, mineral lubricating oil fraction.

6. A grease comprising about 5 to about 12 Weight per cent of an acidic copolymer of an alpha,beta-unsaturated polycarboxylic acid and an aliphatic compound having a terminal vinyl group, said acidic copolymer having a molecular Weight of about 1000 to about 2000, about 5 to about 12 Weight per cent of a saturated aliphatic monocarboxylic acid having 12 to 22 carbon atoms, at least the stoichiometric equivalent of the foregoing of a metal selected from the group of calcium and barium, about 0.5 to about 3 weight per cent of a saturated aliphatic monocarboxylic acid having less than six carbon atoms, at least the stoichiometric equivalent of said monocarboxylic acid having less than six carbon atoms of a metal selected from r the group consisting of calcium and barium, and the balance, to make 100 weight per cent, mineral lubricating oil fraction.

7. A grease comprising about 36 to about 50 parts by weight of an acidic copolymer of an alpha,beta-unsatu rated polycarboxylic acid and an aliphatic compound having a terminal vinyl group, said acidic copolymer having a molecular weight of about 1000 to about 2000 and having a neutralization equivalent of about 150 to about 250, about 25 to about 35 parts by weight of a saturated aliphatic monocarboxylic acid having to 22 carbon atoms, about 5 to about 11 parts by Weight of a saturated aliphatic monocarboxylic acid having less than six carbon atoms, about 7 to about 13 parts by weight calcium suificient to at least neutralize the three acidic components, and the balance, to make about 400 to about 600 parts, mineral lubricating oilfraction.

8. A grease comprising about 50 parts by Weight of an acidic copolymer of maleic anhydride and the allyl ester of a mixture of saturated aliphatic monocarboxylic acids having an average of about 18 carbon atoms, about 50 parts by weight stearic acid, about 7.5 to about 10 parts by weight acetic acid, calcium in amount sufficient to at least neutralize the three acidic components, and the balance, to make about 600 to about 700 parts, mineral lubricating oil fraction.

9. A grease comprising about 50 parts by weight of an acidic copolymer of maleic anhydride and the allyl ester of a mixture of aliphatic monocarboxylic acids hav- 1 ing an average of about 18 carbon atoms, about 35 parts by weight of a mlxture of saturated aliphatic monocarboxylic acids having an average of 18 carbon atoms, about 7 parts by weight of acetic acid, calcium in amount sufficient to at least neutralize the three acidic components, and the balance, to make about 500 to about 600 parts by Weight, mineral lubricating oil fraction.

10. A grease comprising about parts by weight of an acidic copolymer of an alipha,beta-unsaturated polycarboxylic acid and an aliphatic compound having a terminal vinyl group, said acidic copolymer having a molecular Weight of about 1000 to about 2000, about 35 parts by weight of a mixture of saturated aliphatic monocarboxylic acids having an average of 18 carbon atoms, about 10.3 parts by weight or" butyric acid, calcium in amount at least suflicient to neutralize the three acidic components, and the balance, to make about 500 to about 600 parts by Weight, mineral lubricating oil fraction.

11. A grease comprising about 50 parts by Weight of an acidic copolymer of an alpha,beta-unsaturated polycarboxylic acid and an aliphatic compound having a terminal vinyl group, said acidic copolymer having a molecular eight of about 1000 to about 2000, about 35 parts by Weight of a mixture of saturated aliphatic monocarboxylic acids having an average of about 18 carbon atoms, about 7 parts by weight of acetic acid, barium in amount sufficient to at least neutralize the three acidic components, and the balance, to make about 500 to about 600 parts, mineral lubricating oil fraction.

12. A grease comprising about 36 parts by weight of an acidic copolymer of maleic anhydride and l-octadecene, about 25 parts by weight of a mixture of saturated aliphatic monocarboxylic acids having an average of 18 carbon atoms, about 5 parts by Weight of acetic acid, calcium in amount sufiicient to at least neutralize the three acidic components and the balance to make about 400 to about 500 parts by weight mineral lubricating oil fraction.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,976,679 Pikentscher et al Oct. 9, 1934 2,197,263 Carmichael et al Apr. 16, 1940 2,402,825 Lovell et al June 25, 1946 2,417,428 McLennan Mar. 18, 1947 2,417,429 McLennan Mar. 18, 1947 2,417,432 McLennan Mar. 18, 1947 2,417,433 McLennan Mar. 18, 1947 2,483,959 Baer Oct. 4, 1949 2,483,960 Baer Oct. 4, 1949 2,513,680 Shott et al. July 4, 1950 2,533,376 Jones Dec. 12, 1950 2,543,964 Gammaria Mar. 6, 1951 2,564,561 Carmichael et al Aug. 14, 1951 2,577,706 Hotten Dec. 4, 1951 2,615,864 Giammaria Oct. 28, 1952 2,616,849 Giammaria Nov. 4, 1952 2,634,256 Sparks et a1 Apr. 7, 1953 

1. A MODIFIED GREASE COMPRISING A MAJOR PROPORTION OF A LUBRICATING OLEGINOUS VEHICLE, A MINOR PROPORTION OF A MIXED GELLING AGENT AND AN AMOUNT OF AN ALIPHATIC MONOCARBOXYLIC ACID HAVING LESS THAN SIX CARBON ATOMS AND A MOLAR EQUIVALENT OF A METAL OF GROUP II OF THE PERIODIC SYSTEM SUFFICIENT TO PROVIDE A GREASE HAVING A DROPPING POINT OF AT LEAST 300* F., SAID GELLING AGENT COMPRISING A MIXTURE OF SALTS OF A METAL OF GROUP II OF THE PERIODIC SYSTEM AND (1) AN ACIDIC COPOLYMER OF AN ALPHA,BETA-UNSATURATED POLYCARBOXYLIC ACID AND AN ALIPHATIC COMPOUND HAVING A TERMINAL VINYL GROUP, SAID ACIDIC COPOLYMER HAVING A MOLECULAR WEIGHT OF ABOUT 1000 TO ABOUT 2000, AND (2) A SATURATED ALIPHATIC MONOCARBOXYLIC ACID HAVING 10 TO 22 CARBON ATOMS. 